Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L9/00—Rigid pipes
  • F16L9/12—Rigid pipes of plastics with or without reinforcement
  • F16L9/133—Rigid pipes of plastics with or without reinforcement the walls consisting of two layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60T—VEHICLE BRAKE CONTROL SYSTEMS OR PARTS THEREOF; BRAKE CONTROL SYSTEMS OR PARTS THEREOF, IN GENERAL; ARRANGEMENT OF BRAKING ELEMENTS ON VEHICLES IN GENERAL; PORTABLE DEVICES FOR PREVENTING UNWANTED MOVEMENT OF VEHICLES; VEHICLE MODIFICATIONS TO FACILITATE COOLING OF BRAKES
  • B60T17/00—Component parts, details, or accessories of power brake systems not covered by groups B60T8/00, B60T13/00 or B60T15/00, or presenting other characteristic features
  • B60T17/04—Arrangements of piping, valves in the piping, e.g. cut-off valves, couplings or air hoses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/306—Resistant to heat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/308—Heat stability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/18—Applications used for pipes

Definitions

• the invention relates to a tube for a compressed air brake line, which has an outer layer of PA11 or PA12, an inner layer of a zinc chloride-resistant polyamide and optionally an innermost layer of a further zinc chloride-resistant polyamide.
• Compressed air braking systems are often used in heavy-duty vehicles, such. B. in tractors and the like used. In such systems, the braking system is activated by compressed air passing through a pipe.
• Compressed air brake lines are often made from single-layer PA11 or PA12 pipes, as these polyamides have very good resistance to environmental influences; In addition, there are multi-layered solutions. Tissue reinforcement can also achieve a high bursting pressure with good flexibility. In areas with low mechanical and chemical requirements, mainly polyurethane-based systems are used. In particular, the market for semi-trailers and the aftermarket should be mentioned here. These systems are less expensive than systems based on PA11 or PA12, but show significant disadvantages in mechanical strength and chemical resistance.
• a compressed air brake line which consists of a tube with the layer sequence PA11 or PA12 / adhesion promoter / impact modified PA6 or PA66 exists; If appropriate, this is followed by a further adhesion promoter layer and a final layer of PA11 or PA12.
• the tube of the US Pat. No. 6,670,004 have the layer sequence PA612 / impact-modified PA6 or PA66 / PA612.
• a tube with a corresponding layer structure, but in which the PA6 or PA66 of the inner layer contains no Schlagzähmodifier is from the US 2009/0065085 A1 known.
• the object of the present invention is to avoid the abovementioned disadvantages, and in particular to provide a tube which meets the requirements placed on a compressed air brake line with regard to resistance to chemicals, motor oils, zinc chloride and road salt and a high bursting strength even at elevated Temperature, has a good low-temperature impact resistance and a good aging resistance.
• these layers directly follow one another; So there is no intermediary adhesive layer used here.
• the outer layer based on PA11 and / or PA12 in this case ensures a very good zinc chloride resistance of the compressed air brake line compared to a line which consists entirely of a molding compound according to layer II.
• a monotube of a PA612 molding compound would not be in accordance with the invention because PA612 has a lower zinc chloride resistance than PA11 or PA12.
• the outer diameter of the tube is usually in the range of 6 to 20 mm, and preferably in the range of 7 to 16 mm, while the wall thickness may be 1.0 to 2.0 mm.
• the thickness of the layer II is in this case 25 to 90%, preferably 30 to 80% and particularly preferably 35 to 70% of the wall thickness, while the thickness of any adhesion promoter layers present in each case 0.02 to 0.2 mm, preferably 0.04 to 0, 16 mm and more preferably 0.06 to 0.14 mm. Any existing adhesion promoter layers are preferably thinner than the respective adjacent outer layer or innermost layer.
• the polyamide of layer II can be prepared from a combination of diamine and dicarboxylic acid, from an ⁇ -aminocarboxylic acid or the corresponding lactam.
• the ⁇ -aminocarboxylic acid or lactam contains at least 8, at least 9 or at least 10 C atoms.
• the arithmetic mean is considered here.
• the arithmetic mean of the C atoms of diamine and dicarboxylic acid must be at least 8, at least 9, or at least 10.
• Suitable polyamides are, for example: PA610 (preparable from hexamethylenediamine [6 C atoms] and sebacic acid [10 C atoms], the average of the C atoms in the monomer units here is 8), PA88 (preparable from octamethylenediamine and 1.8-octanedioic acid) , PA8 (made from capryllactam), PA612, PA810, PA108, PA9, PA613, PA614, PA812, PA128, PA1010, PA10, PA814, PA148, PA1012, PA1014 and PA1212.
• PA610 preparable from hexamethylenediamine [6 C atoms] and sebacic acid [10 C atoms], the average of the C atoms in the monomer units here is 8
• PA88 preparable from octamethylenediamine and 1.8-octanedioic acid
• PA8 made from capryllactam
• copolyamides based thereon can also be used, it also being possible to use monomers such as caprolactam provided that the mean of the number of C atoms adheres to the above condition.
• the polyamide of layer II can be prepared from a combination of diamine and dicarboxylic acid.
• the polyamide may also be a polyetheresteramide or a polyetheramide.
• Polyetheramides are in principle z. B. from the DE-OS 30 06 961 known. They contain as comonomer a polyether diamine. Suitable polyetherdiamines are obtainable by conversion of the corresponding polyetherdiols by reductive amination or coupling to acrylonitrile with subsequent hydrogenation (eg. EP-A-0 434 244 ; EP-A-0 296 852 ). They usually have a number average molecular weight of 230 to 4000; their proportion of the polyetheramide is preferably 5 to 50 wt .-%. Commercially available polyether based on propylene glycol as ELASTAMIN ® grades at the company.
• polyetherdiamines based on 1,4-butanediol or 1,3-butanediol or mixed polyetherdiamines, for example with random or with blockwise distribution of the units derived from the diols, are also very suitable.
• the hard block of the polyetheresteramide or polyetheramide is formed from a low molecular weight polyamide as defined for layer II above.
• the polyamide of layer II has a crystallite melting point T m , measured by DSC according to ISO 11357 during the second heating, of at least 182 ° C, more preferably of at least 188 ° C, particularly preferably of at least 195 ° C and very particularly preferably at least 200 ° C.
• the molding compound of layer II may additionally comprise PA11 or PA12 in addition to the above-defined polyamide, in which case polyetheresteramides or polyetheramides are included.
• PA11 or PA12 in addition to the above-defined polyamide, in which case polyetheresteramides or polyetheramides are included.
• the layer III consists in a first embodiment as the layer I of a molding composition based on PA11 and / or PA12. In a second embodiment it consists, like layer II, of a polyamide-based molding composition whose average monomer units contain on average at least 8, at least 9 or at least 10 C atoms, PA11 and PA12 being excluded. In a third embodiment, the layer III consists of a molding composition based on a mixture of polyamide whose monomer units contain on average at least 8, at least 9 or at least 10 carbon atoms, and PA11 and / or PA12.
• the molding compositions of the individual layers are generally well compatible with each other, so that no adhesion promoter layers are necessary. Compatibility can be further improved if at least one of the layers contains a polyolefinic compound having acid or acid anhydride groups, for example one of the impact modifiers listed below. Thus, the number of layers can be reduced, which makes the production less expensive.
• a suitable adhesion promoter is, for example, a molding compound based on a polyamide, which is sufficiently compatible with the materials of the two adjacent layers, or based on a mixture of the polyamides present in the adjacent layers.
• the adhesion-promoting effect can be increased if the adhesion promoter additionally contains an impact modifier which, as usual with polyamide molding compositions, carries acid anhydride groups, for example an ethylene-propylene rubber functionalized with maleic anhydride or an ethylene-acrylic ester-maleic anhydride terpolymer.
• Further suitable adhesion promoters are maleic anhydride or acrylic acid functionalized polyolefins are commercially available under the tradenames ADMER ® or BYNEL ®.
• the molding compositions of the individual layers generally contain further components, such as.
• impact modifiers other thermoplastics, plasticizers and other conventional additives that are needed to adjust certain properties.
• examples include pigments or fillers such as carbon black, titanium dioxide, zinc sulfide, silicates or carbonates, processing aids such as waxes, zinc stearate or calcium stearate, flame retardants, glass fibers, Antioxidants, UV stabilizers and additives that give the product anti-electrostatic properties or electrical conductivity such.
• carbon fibers graphite fibrils, stainless steel fibers or conductive carbon black.
• Suitable toughening modifiers are those commonly used for polyamide molding compositions, such as maleic anhydride functionalized ethylene-propylene rubber, maleic anhydride functionalized styrene-ethylene / butene block copolymers, acrylate rubber, and the like.
• plasticizers suitable conventional compounds are, for. B. esters of p-hydroxybenzoic acid having 2 to 20 carbon atoms in the alcohol component or amides of arylsulfonic acids having 2 to 12 carbon atoms in the amine component, preferably amides of benzenesulfonic acid.
• plasticizers come u. a. ethyl p-hydroxybenzoate, octyl p-hydroxybenzoate, i-hexadecyl p-hydroxybenzoate, n-octyl toluene sulfonamide, benzenesulfonic acid-n-butylamide (BBSA) or benzenesulfonic acid 2-ethylhexylamide.
• a phosphorus-containing flame retardant can be used, for example, a phosphate or phosphonate, such as. B. diphenyl cresyl phosphate.
• thermoplastics which may be included in the molding compositions of the individual layers are, for example, polyolefins which are preferably functionalized with maleic anhydride or the like or a non-demanding polyamide such as PA6 or PA66.
• the molding compound of the outer layer I contains a copper-containing stabilizer.
• both the molding composition of the outer layer I and the molding compound of the inner layer II contain a copper-containing stabilizer, wherein particularly preferably no layer III is contained here.
• both the molding composition of the outer layer I and the molding compound of the innermost layer III contains a copper-containing stabilizer.
• both the molding compound of the outer layer I, the molding compound of the inner layer II and the molding compound of the innermost layer III contain a copper-containing stabilizer.
• suitable copper compounds are copper salts such as copper chloride, copper bromide, copper iodide, copper acetate, copper stearate or copper acetylacetonate.
• the use of such copper-containing stabilizers in polyamide molding compounds is prior art; corresponding stabilizer systems are commercially available.
• the copper-containing stabilizer is preferably used in an amount such that the stabilized polyamide molding compound has a copper content, calculated as Cu, in the range of 0.001 wt% to 0.05 wt%, and more preferably in the range of 0.002 wt% to Has 0.03 wt .-%.
• a higher copper content improves stabilization only to a minor extent, while it may be distracting due to the intrinsic color of the copper.
• the stabilizing effect is insufficient.
• the copper-containing stabilizer can be used according to the invention together with an organic stabilizer.
• Corresponding mixed stabilizer systems are commercially available.
• the copper-containing stabilizer achieves long-term stabilization against loss of mechanical properties at high continuous use temperatures and efficient processing stabilization against polymer degradation.
• the compressed air brake line according to the invention may have, for example, the layer configurations indicated in the table.
• the polyamides on which the molding compositions are based and the copper-containing stabilizer which may be present are stated here.
• the tube may include prior art fabric reinforcement. This can be either within a layer or between two layers. From the manufacturing point of view, the application of the fabric layer to the outer layer of the pipe with subsequent rubber coating is technically the simplest to realize. As rubber comes here either a vulcanizable rubber in question or a thermoplastic elastomer such. B. Santoprene. The coating with rubber can also be done without a fabric layer is applied.
• the pipe according to the invention is used as a compressed air brake line, such as in trucks, trailers, trailers for trucks or trailers.
• the lines are usually operated with an operating pressure of up to 12.5 bar, on trailers or trailers with 8.5 bar.
• Table 1 ⁇ / u> Sample Layer Configurations Outer layer I Bonding layer Inner layer II Bonding layer Innermost Layer III 1 PA 12 - PA612 - - 2 PA12, Cu stabilized - PA612 - - 3 PA12, Cu stabilized - PA612, Cu stabilized - - 4 PA12, Cu stabilized - PA612 - PA12, Cu stabilized 5 PA12, Cu stabilized - PA612, Cu stabilized - PA12, Cu stabilized 6 PA11, Cu stabilized - PA612 - - 7 PA11, Cu stabilized - PA612, Cu stabilized - - 8th PA11, Cu stabilized - PA612 - PA11, Cu stabilized 9 PA11, Cu stabilized MSA-modified
• VESTAMID ® X7393 was used because it contains slightly less impact modifiers and plasticizers as the VESTAMID ® LX9013 and thus monopipes were obtained that have almost the same flexibility as the three-layer tube of Example 1. Fig. This ensured comparability of the results.
• VESTAMID ® X7393 is a standard molding compound for the manufacture of compressed air brake lines.

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• Engineering & Computer Science (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Transportation (AREA)
• Laminated Bodies (AREA)
• Braking Arrangements (AREA)
• Rigid Pipes And Flexible Pipes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2013
  • 2013-05-16 DE DE102013209126.5A patent/DE102013209126A1/de not_active Withdrawn
• 2014
  • 2014-04-24 EP EP14165827.8A patent/EP2842736A1/fr not_active Withdrawn
  • 2014-05-13 US US14/276,158 patent/US20140338780A1/en not_active Abandoned
  • 2014-05-13 BR BRBR102014011467-0A patent/BR102014011467A2/pt not_active IP Right Cessation
  • 2014-05-13 IN IN2390CH2014 patent/IN2014CH02390A/en unknown
  • 2014-05-14 RU RU2014119268/04A patent/RU2014119268A/ru not_active Application Discontinuation
  • 2014-05-15 MX MX2014005914A patent/MX2014005914A/es unknown
  • 2014-05-15 CN CN201410204634.9A patent/CN104165251A/zh active Pending
  • 2014-05-15 KR KR1020140058277A patent/KR20140135643A/ko not_active Application Discontinuation
  • 2014-05-16 JP JP2014102133A patent/JP2014224607A/ja not_active Withdrawn

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